This work reveals energy-transfer mechanisms in lanthanide-based materials, suggesting better optical performance.
Understanding and tuning the luminescent properties of lanthanide(III) ions is of great interest for a range of optical applications, for example photo down-shifters for photovoltaics. In this work a series of isostructural polyoxotitanates (POTs) of general formula Ln2Ti4O6(phen)2(met)10 (Ln2Ti4, Ln = Nd, Sm-Er, Yb, met = methacrylate) was synthesized, where the lanthanide is coordinated to a titanium-oxo core and the antenna ligand 1,10-phenanthroline (phen). The energies of the ligand S1 and T1 states in the Ln2Ti4 series were determined, which, together with the luminescence spectra of the Ln2Ti4 compounds, gave new insights into the intramolecular energy-transfer mechanism and efficiencies between the ligand periphery and the Ln3+ ions. The effect of the rigidity of the Ti4O6-core on the coordination environment of a lanthanide was quantified for the first time using lifetime measurements, which shows a significant increase of Δτ = 1.1 ms for Eu2Ti4 compared to the reference Eu2(phen)2(met)6 (Eu2), in which no metal-oxo core is present. This key finding illustrates the advantage in designing lanthanide-based lumiphores containing rigid metal-oxide cores.
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Müller et al. (2025) studied this question.
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